This invention relates to gas-discharge lamps that produce electromagnetic radiation in the ultra-violet region of the electromagnetic spectrum. Such lamps may find use in various applications relating to disinfection, such as for the purification of water or treatment of food and beverages, in the manufacture of pharmaceuticals and also for curing and drying. More specifically, the invention relates to a mercury-free gas-discharge lamp and, in particular, a mercury-free radiation source for a gas-discharge lamp.
In a typical gas-discharge lamp, ultra-violet (UV) light is generated by passing an electrical discharge through an ionised gas (or “plasma”), as a consequence of the resulting transitions of electrons between energy states emitting photons of particular energies.
The use of ultra-violet (UV) electromagnetic radiation or light for disinfection and purification purposes is known. The most desirable wavelengths of UV radiation for disinfection purposes are generally understood to be in the 180 nm to 320 nm range, more preferably 200 nm to 300 nm (often referred to as UV-C), and optimally around 265 nm. UV radiation of such wavelengths has both a biological effect, inactivating (if only temporarily) micro-organisms primarily by genomic damage preventing replication, and a chemical effect, breaking chemical bonds (including those of micro-pollutants) by a process called photodissociation or photolysis.
UV electromagnetic radiation, typically of slightly higher wavelengths (up to approximately 400 nm), is also used for curing and drying.
Conventional UV gas-discharge lamps comprise an elongate tube of quartz or silica with electrodes at either end. The lamps are filled with a starting gas, typically a noble gas such as argon or xenon, and also a small quantity of radiating working material, typically mercury. At room temperature most of the mercury inside the lamp is in liquid form. The lamp is ignited by passing an electrical current across the electrodes of the lamp, which ionises the starting gas, the resulting atomic/electron collisions causing the mercury to evaporate. Once the lamp has reached operating condition, the mercury partial pressure is much higher than that of the starting gas, and mercury therefore dominates the electrical and radiating behaviour of the lamp.
There follows a short overview of high-pressure, low-pressure and metal-halide discharge lamps.
Overview of UV Sources
The development of sources of UV radiation is entwined with the development of sources of Electromagnetic Radiation (ER) in the visible spectrum i.e. visible lighting. These associations are not only in respect to the same fundamental principles of physics and design but practically as well. A key example being that of the low-pressure mercury (LP Hg) lamp which is essentially identical to that of a fluorescent lamp used commonly for residential lighting except for the addition of a phosphor coating which absorbs the UV atomic emission of mercury, and then subsequently emits in the visible region. As visible lighting consumes approximately 25% of the worlds produced electrical energy the goals for increased efficiency and extended lifetimes of visible ER sources are also aligned providing potential insight into an alternative method of UV ER generation. Sources of UV radiation are investigated and discussed below, however particular focus has been given to plasma sources, because of their current dominance of the market. Emerging sources and their impacts are also discussed.
Plasma UV Radiation Sources
Plasma lamps achieved commercial success in the 1930's following on from the incandescent lamp, where an incandescent lamp emits ER from a hot body e.g. a tungsten wire.
A plasma lamp (plasma being defined for example as “a gaseous mixture of positive ions and electrons”) provides several benefits over an incandescent lamp. Firstly, radiation is produced with increased energy efficiency (i.e. the ratio of energy output to energy input). Secondly, as plasma-derived photons are produced from direct atomic excitation, their wavelengths are determined by the atomic constituents of the plasma, thus enabling the production of UV radiation. A number of methods have been developed to use plasma to produce UV radiation. The historically most successful methods are summarised below (physical characteristics such as lamp size, electrode design etc can vary considerably depending on the plasma characteristics, however these are not discussed. Instead focus is given to the variation in plasma characteristics):
Low Pressure (LP) Discharge Lamps
To produce suitable lamp plasma for use in UV disinfection an element or compound, the following characteristics must be achieved:                Relatively low ionization energy whilst having an excitation energy to produce resonance ER at desirable wavelengths        Sufficient vapour pressure to produce optimal internal lamp pressures whilst having a low enough boiling temperature to be in gas/vapour phase whilst at lamp operating temperatures        Chemically inert to lamp materials i.e. electrodes and lamp envelope        
Mercury (Hg) meets these criteria and hence is the primary constituent of the majority of lamp plasmas for both visible lighting and UV disinfection. Although other elements can be and are used in limited quantities e.g. xenon, practical challenges include high internal lamp pressure creating problems when starting the lamp, and high running currents. Lamp pressures for compact Xenon lamps being in the region of 15 atm cold and up to 60 atm when running with the relevant temperature increase.
The Low Pressure (LP) Hg plasma discharge lamp is composed of a low internal Hg gas pressure (approximately 0.01 mbar) combined with a buffer gas that is usually argon. The low Hg pressure ensures that the majority of electron excitations are at two energy transitions producing 253.7 nm and 185.0 nm. The Hg pressure (and therefore the impedance and consequentially the lamp power) is determined by the running temperature of the lamp (increasing temperature meaning increasing pressure) and regulating the amount of Hg in the gas phase to that condensed on the cold spot, as shown in FIG. 1. The cold spot is the coldest point in the lamp and as such the point at which mercury will condense. More commonly, the practice of using a mercury amalgam (such as with bismuth or indium) enables better regulation of Hg in the gas phase (i.e. better stability) and enables an increase in power density, although secondary implications of this are a reduction in radiant efficiency in part due to the absorbance of resonance emission.
FIG. 1 shows a diagrammatic representation of key features of a Low Pressure mercury discharge lamp.
With the optimal selection of lamp variables (i.e. lamp geometry, Hg content, temperature etc.) an energy efficiency of 60% at 253.7 nm can be achieved, however this is only at low power densities (<0.5 W/cm approx. 0.2-0.3 W/cm at 253.7 nm); increasing power densities by up to 400% with the use of an amalgam and increasing tube diameter (in the region of 26-33 mm) will reduce the lamp efficiency to the region of 36% at 253.7 nm. Even at the highest efficiency, 40% losses are incurred which can be attributed to: the production of other wavelengths (3%), losses at the electrodes (15%) and elastic collisions with the tube wall and argon (22%). With such a temperature sensitive design, a limitation can be the temperature of the surrounding water, which, if at 4° C., would reduce the radiant efficiency to approximately 20%.
The development trend in LP discharges is to increase power density whilst maintaining radiant efficiency. In addition to the adoption of amalgam as previously described, the selection of the lamp driver is critical and further efficiencies have been gained by the use of a high frequency driver with a square wave. During the mid-1970's the concept of active heat regulation of the lamp through heating of the cathode and external heating of the lamp was employed, enabling optimised lamp conditions and therefore increased power densities (in part due to a reduction of re-absorption through line broadening). This concept has recently been reapplied to provide an increased output for UV disinfection reiterating the desire for a high radiant efficiency and high power density UV source. Further developments in lamp driver electronics have seen the use of inductively coupled fluorescent lamps and are proposed as a future solution to enable further continuing improvement of the LP plasma lamp, by reducing net losses and extending lamp life by removing the need for electrodes.
High Pressure (HP) Discharge Lamps
The basic requirements for a High Pressure (HP)—a term which includes High Intensity Discharge (HID)—in terms of lamp fillings are the same as that of the LP discharge, and hence Hg is again the most commonly used filling. In contrast however, the amount of Hg (and hence consequentially the internal pressure) is significantly higher than that of a LP discharge and as a key distinction to that of the LP discharge, all the Hg is in the vapour phase. This is shown in FIG. 2 to illustrate this contrast to the LP discharge displayed in FIG. 1.
FIG. 2 shows a diagrammatic representation of key features of a High Pressure mercury discharge lamp.
As in the LP discharge, an increase in Hg vapour pressure increases impedance, hence increasing voltage (V) and consequentially power density of the lamp. The pressure gradient is continuous between a LP and HP discharge however a clear distinction is made to that of a HP discharge when the temperature of the (Hg) ions and electrons reach an (approximate) equilibrium referred to as a Local Thermal Equilibrium (LTE) as shown in FIG. 3. The temperature equality between atom/ion and electron is due to increased elastic collisions occurring because of increasing pressure. This produces numerous fundamental changes to the way the lamp functions, two key distinctions being the radiant efficiency and spectral output.
FIG. 3 shows the relationship between the temperature of Hg atoms/ions and electrons in relation to pressure.
Losses in elastic collision are proportional to the difference between a low energy electron to that of a high energy atom/ion (ie. LP discharge atom/ion temperature in the range of 300K to 700K and electron temperature above 10,000K. HP discharge has both atom/ion temperature generally between 4,000K and 11,000K depending on lamp conditions, meaning that when LTE is reached, elastic losses approach zero. Additionally, as power density increases so does the temperature of the lamp and in particular the arc which develops in the high pressure lamp, enabling thermal excitation and its subsequent emission. Although the lamp temperature increases, the thermal losses are not surprisingly low due to the low thermal conductivity of Hg. The implications being the LTE provides disproportionate radiant efficiency benefits to the HP discharge in comparison to that of the LP discharge. The arc develops because of a radial temperature gradient within the lamp; as temperature increases so does ionization (producing electrons referred to as current carriers) meaning that the current density is highest at the axis of the electrodes. This means that the LTE as a consequence has a significant increase in net radiant efficiency (FIG. 4). The stages displayed in FIG. 4 show the transition between the optimal LP discharge (labelled 2) to reduction in efficiency with increasing pressure/power to that more commonly used in UV reactors (between points 2 and 3) and the increasing efficiency of the HP discharge at the most common pressure region i.e. medium pressure UV lamps (labelled 4).
FIG. 4 shows the luminous efficiency of a mercury plasma discharge in relation to pressure.
The second implication of increasing pressure and plasma temperature is that of changing spectral output. The LP discharge is dominated by atomic collision and spectral emission from excitation, hence the two narrow and dominant emission lines at 253.7 nm and 185 nm, this changes with increasing pressure, which is thought due to:                1. Additional excitations occur from excited states to greater energy levels, producing numerous further emitted photons at different wavelengths        2. Ionization occurs when subsequent excitations exceed atomic energy levels and a photon is then emitted on atom/ion recombination (contributing to spectral continuum's e.g. 200-230 nm Hg continuum        3. Bremsstrahlung—the process by which photons are emitted during acceleration or deceleration within the plasma (also producing a continuous spectrum)        
Therefore the HP discharge can be characterised by a high density high efficiency discharge with a spectral output form the UV to the Infra-Red (IR). Although the spectral output far exceeds that of LP discharge, the plasma efficiency enables the total radiant efficiency to be approximately ⅓ of that of a LP discharge. With similar advances in high frequency electronic drivers as for the LP discharge, the expected lamp life can be between 2,000 to 8,000 hours dependent on lamp design parameters. The practical implications means that compared to a LP discharge a far higher UVC density can be achieved in more efficient discharge in respect to radiant efficiency, however a compromise is made with a lower spectral efficiency.
Metal Halide (MH) Lamps
The efficiency of the HP plasma cannot be optimised or improved by pressure control as discussed for the LP discharge because it already functions in the LTE. However in visible lighting a resourceful method has been employed to enable the use of elements with desirable excitation and ionization energies but with too high a boiling point or too low a vapour pressure. The use of a halogen in conjunction with a desirable element will in most cases result in the reduction of the boiling point, enabling it to be used as directly or as part of a HP plasma. Iodine is often the selected halogen over bromine and chlorine as it is less reactive with internal lamp components whilst also generally producing the highest vapour temperature compared to other halogen compounds. The halide (in addition to the halogen component) is usually metal and hence the term Metal Halide (MH) is/are added to a high pressure Hg discharge. The Hg then performs the role of a ‘buffer gas’ which provides majority of the required gas vapour and electrical properties, although in this case does also contribute to the spectral output. The spectral output is almost entirely determined by the additional metal content73 due to the fact the excitation potential of the metals used are comparatively much lower than Hg (FIG. 5). Although in most respects such a plasma can be considered similar to a pure Hg HP discharge the added halides can have a disproportional effect on lamp running conditions such as the size of the arc, both arc broadening and narrowing impacted by the electron carrying capacity.
FIG. 5 shows a diagrammatic representation of key features of a metal halide and mercury lamp.
The lower vapour temperatures provided by the metals used in their halide form enables them to be in the vapour phase whilst at the operational temperatures of the lamp. As the temperatures increase towards the arc the halide dissociates and associates at lower temperatures at the lamp wall (FIG. 6). When the halide is disassociated at the lamp arc, excitation of both the metal and halogen is possible, however due to the higher energy potentials of the halogen practically no excitation energy is emitted, meaning the output is dominated by the spectral characteristics of the metal rather than the Hg or halogen.
FIG. 6 shows a diagrammatic representation of halide cycle from lamp wall to lamp arc.
The MH lamp appears in many ways to be the ideal solution to the limitations of low power densities or low spectral efficiencies associated with the LP and HP discharges respectively. In fact, the potential for MH lamps to produce spectral efficiencies (visible region) of 34% and enhance colour rending facilitated its entry into the lighting market. The ability of MH lamps to be used for UV generation is limited. Experiments on iodide additives (iron (FeI2), cobalt (CoI2), manganese (MnI2), antimony (SbI2)) to assess their impacts on UV outputs, and although FeI2 and MnI2 enhanced the UVA output, none of the iodides improved the output in the UVC region. Presumably this limitation is associated with the need for a lower excitation potential required for effective MH operation.
Although the MH lamp provides highly desirable spectral and electrical characteristics, numerous practical problems were encountered and had to be overcome before commercial MH lamps were widely produced. One such limiting factor for the high intensity discharge (HID) is lamp life, which is closely associated with the high temperatures and small lamp geometry. One benefit of a lamp running at a temperature above 500° C. is that the absorption band at 215 nm which develops with time in quartz is removed. The absorption (thought to be due to loss of oxygen from the silica lattice) is removed by heating above 500° C. and thus a lamp with a quartz envelope running at or above this temperature is assumed to reverse such a formation. As a MH lamp is designed with much smaller geometries and higher pressures, a geometry and pressure similar to that of a MP lamp is likely to gain the benefits of a HP discharge without the geometry related issues of a visible HID lamp.
UV Source Selection
Low pressure (LP) and high pressure (HP) mercury (Hg) lamps dominate the UV disinfection market due to their relative operating simplicity and reasonable energy efficiency. Numerous improvements have been made in LP lamps, however their greatest limitation is internal losses caused by its low internal pressure. Improvements have also been made to HP lamps however ultimately their limitation in further efficiency improvements are related to the spectral output, determined by the lamp pressure.
To meet the needs of a high efficiency and high density lamp, the metal halide (MH) lamp has been proposed due to its success in visible lighting, and if the concept could be successfully applied to UV generation it would provide a desirable solution. The present work identifies one limitation of prior attempts as relating to the reliance upon Hg as the primary lamp filling which restricts the use of MH components with spectral lines of higher energy and therefore optimisation of spectral output in the UVC region.
Preferred performance objectives to enable widening of the upper energy density range of disinfection applications of the lamp include:                1. An optimised spectral output between 200-230 nm and 260-280 nm        2. Ability to run on a conventional lamp driver i.e. electromagnetic or electronic mercury/metal halide ballast        3. Closely matched geometrical dimensions of a medium pressure Hg lamp        4. A germicidal radiant efficiency better than that of an equivalent Hg based lamp        
To warrant switching from a traditional Hg based HP lamp it would be preferable to offer a competitive advantage i.e. increased germicidal efficiency. An approximate figure of 12% germicidal efficiency is typical for a Hg HP lamp; however, efficiency will be related to lamp diameter i.e. the losses incurred from photon production at the lamp arc to that of emission of the lamp wall. Thus 12% can be used as a guideline figure but a direct efficiency comparison of any proposed lamp to a Hg lamp of equal diameter would need to be conducted.
Desirable performance objectives include:                1. A germicidal radiant efficiency of 20% or greater        2. The ability to select an increased area of spectral output i.e. at 200-300 nm or 260-280 nm        3. No Hg lamp fillings        4. A germicidal power density equal to or greater than a conventional medium pressure Hg lamp        
These design characteristics are specifically of a narrow scope to enable a design concept and investigation to be undertaken. Additional performance data will relate to specific applications (including but not necessarily exclusive to water disinfection), comprising for example a detailed assessment including the effect on whole life costs (inclusive of lamp costs, lamp driver and combined efficiency) and specific application considerations such as the production of disinfection by-products (DBP).
To achieve the specified performance aim and objectives of the lamp the proposed concept is to produce a MH lamp with a dominant UVC output. This has been selected as a design concept as it is an adaptation of an existing approach used in visible lighting and is principally a high density discharge as required to meet the design objectives.
Potential reasons for selecting the concept of a UVC MH lamp may include the following:                Production of a HP discharge reduces the energy lost thermally in proportion to energy emitted as radiation, i.e. a benefit of a high pressure discharge        The selection of an element (as part of a primary halide) that is spectrally preferential in both spectral and transitional lines than Hg and/or excitation energies are suitably low enough to enable a secondary halide with ideal excitation energies/spectral lines, i.e. the spectral benefits of the low pressure discharge        Producing a suitable plasma from the MH or combination of MH to enable a stable arc and suitable plasma resistance to enable desired power densities i.e. mimicking power densities and electrical characteristics achieved currently by medium pressure Hg lamps        
Attempts to enhance the UVC spectral output of a Hg based MH lamp have not been successful to-date. One possible cause of this lack of success could be because of the previous selection of elements e.g. antimony which has preferential spectral lines that have a higher excitation energy than Hg and thus not favoured, as was seen for elements with lower excitation energies, e.g. iron. Therefore an alternative primary lamp filling is proposed which has similar physical characteristics to Hg whilst also having lower spectral lines (i.e. higher photon energies) than the lowest desired spectral region i.e. 200-230 nm. A suitable secondary lamp filling preferably has desirable excitation energies (spectral lines) and ionization energies, whilst providing functional vapour pressures both at lamp starting and running temperatures.
The minimum vapour pressure to produce useful radiation at 1000K (726.85° C.) is 133 Pa (1 torr) with possible elements to meet this condition being strontium, tellurium, magnesium, zinc, cadmium and caesium. Using an element in halide form in general increases vapour pressure, reduces the boiling temperature and metal iodides do not appreciably react with the fused silica such as magnesium and zinc.
The halide(s) and ideally iodide(s) preferably meet a number of criteria. The primary halide should ideally mimic the vapour pressure characteristics of Hg whilst having dominant spectral lines lower than 253.7 nm (i.e. a higher energy) enabling a secondary halide with a suitably high enough vapour temperature not to impact lamp characteristics, whilst having spectral lines of a desirable wavelengths 200-230 nm and/or 260-280 nm to be preferentially selected in excitation. The halide also preferably needs to be stable at lamp wall temperatures and dissociate at arc temperatures (4000-6000K). Consequentially a spectral and functional assessment of primary and secondary lamp fillings is required to enable a lamp concept to be developed.
According to a first aspect of the invention there is provided a mercury-free high-pressure metal-halide ultraviolet gas-discharge lamp comprising a primary filling of at least one of osmium, germanium and tellurium, and a secondary filling comprising at least one of tin, antimony, indium, tantalum and gold.
Preferably, the primary lamp filling is tellurium and the secondary lamp filling is antimony.
Preferably, the halogen of the metal-halide comprises iodine.
Preferably, the primary lamp filling is TeI2 and the secondary lamp filling is SbI3.
Preferably, the ratio of iodine to tellurium is non-stoichiometric, preferably with a reduced iodine content.
Preferably, the ratio of iodine to tellurium is no greater than 2:1, preferably no greater than 1.5, more preferably less than 1.0. The ratio may be by mass in gaseous form.
Preferably, the lamp output comprises electromagnetic radiation of wavelength in the range 200-300 nm.
Preferably, the primary lamp filling has similar physical characteristics, such as vapour pressure, to mercury whilst also having lower spectral lines (i.e. higher photon energies) than the lowest desired spectral region i.e. 200-230 nm, more preferably having dominant spectral lines lower than 253.7 nm.
Preferably, the secondary lamp filling has suitably high enough vapour temperature not to impact lamp characteristics, both at lamp starting and running temperatures, whilst having spectral lines of a desirable wavelengths 200-230 nm and/or 260-280 nm to be preferentially selected in excitation.
In some embodiments, alternative enclosure materials other than quartz may be used, such as (but not limited to) ceramic materials. This may reduce if not eliminate the effects of the lamp filling otherwise reacting with the lamp body material.
In some embodiments, the lamp may be driven without the use of electrodes, for example inductively or with the use of microwaves. This may limit the effects of material reactions which may arise, for example, when using tungsten based electrodes and/or iodine in the fillings.
Further features of the invention are characterised by the dependent claims.
Any apparatus feature as described herein may also be provided as a method feature, and vice versa.